Orange to brown disazo dyes and method of preparing same



Patented Aug. 13, 1929.

UNITED STATES PATENT OFFICE.

HENRY JORDAN, OF WILMINGTON, TELAWARE, ASSTGNOB TO E. I. DU PON'I. DE

NEMOURS & COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELA- WARE.

ORANGE TO BROWN DISAZO DYES AND METHOD OF PREPARING SAME.

No Drawing. Application filed November This invention relates to disazo dyes for cotton and the method of preparing the same. More particularly it is concerned with orange to brown dyes with a marked affinity for cotton and their preparation by coupling diazo compounds not having a sulpho or carboxy group with an amino-benzoyl-amido-benzoyl-2-amido -5- naphthol 7 sulphonic acid, diazotizing the, resulting monoazo compound and combining it with a sulpho or carboxyl-aryl-pyrazolone compound or a sulpho or carboxyl indole compound.

The Reissue No. 13,304 of U. S. P. 994,420 describes the manufacture of certain aminobenzoyl-ainido-benzoyl-Q-amido-5-naphthol 7-sulphonic acid compounds; which compounds have an afiinity for the cotton fibre. It has now been found that valuable orange to brown disazo dyes for cotton can be made by using these intermediates as middle com: ponents. The dyes prepared in this way have the constitution: R -N=Nbenzoylan l (COOH) The process can best be disclosed by the presentation of a numberot examples of actual embodiments thereof. It is to be understood, of course, that these examples are 13,1925. Serial No. 68,920.

amido benzoyl 2 amido 5 naphthol 7.- sulphonio acidN=NR R being an aryl radical without a sulpho or carboxy group and It, being a grouping containing a sulpho or carboxy aryl pyrazolone radical or a sulpho or carboxy indole radical. In spite of the fact that they are comparatively soluble, these dyes show an extraordinary fastness to Washing, which is nearly as good as that shown by developed dyes. They discharge to a pure white with hydrosulphite.

As first components (from which radical R is derived) there may be used, for instance, aniline, ortho, meta or paratoluidine, Xylidine, ortho or para-.anis'idine, chloroaniline, alpha or 'beta-naphthylamine, etc.

On reduction with stannous chloride these dyes will yield amino derivatives corresponding to the first components used, Q-(aminobenzoyl amido-benzoyl-amido) -5-hydroXy-6- amino-naphthalene-7-sulphonic acid and either amino-pyrazolone or amino-indole sulpho or carboxy acids of the type:

d o-onl sous NH 00011) in 2000 parts of water and 400 parts of 50- dium carbonate, keeping the coupling temperature at 15 C. The dye is precipitated from the partly colloidal solution with salt. In its dry form it is a dark orange powder. It d es cotton from an alkaline 5 salt bath or laubers salt bath in bright SOzH OM On reduction with stannous chloride. this dye will yield aniline, 2- (p-amino-benzoyl-pamido benzoyl-amido) -5-hydroxy-6-amino naphthalene-'I-sulphonic acid, and p-sulphophenyl-methyl-amino-pyrazolone:

E-o-om Ezmmple 2.Using instead of 254 parts of On reduction with stannous chloride this dye will yield aniline, Q-(p-amino-benzoylp amido benzoyl amide) 5 hydroxy- 6-amino-naphthalene-7-sulphonic acid and amino-methyl-ketole-sulphonic acid SOIH NH Example 3.-Using' 121 parts of m-xylidine instead of 93 parts of aniline (as in Example 1 leaving all other conditions the same, a re der shade of orange is obtained son:

On reduction with stann'o'us chloride this dye will yield alpha-naphthylamine, 2-(pyellowish-orange shades, which show a good fastness to light and a remarkable fastness to washing. Discharging with hydrosulphite gives a pure white. The dye has probably the formula:

p-sulpho-phenyl-methyl-pyrazolone (as in Example 1) 211 parts of methyl-lietole-sulphonic acid:

\CCH: son: NH/

and leaving all other conditions the same as in Example 1 a somewhat redder orange is obtained, the other properties of the dye being similar to those of Example 1. The dye has probably the formula:

(I -CH:

3 N-OSOQI amino-henzoyl-p-amido-benzoyl-amido) 5 hydroxy-6-amino-naphthalene 7 sulphonic ,acid, and p-sulpho-phenyl-methyl-aminopyrazolone:

n-o on,

Instead of the p-amino-benzoyl-p-amidobenzoyl-2-amido-5-naphthol-7-sulphonic acid there may be used the meta-meta, parameta, or meta-para-amino-benzoyl compound. Instead of the p-sulpho-phenylmethyl-pyrazolone other sulpho or carboxy pyrazolones may be used, as p-carboxyphenyl methyl pyrazolone, chlor sulpho phenyl-, sulpho-naphthyl-pyrazolones, etc. Or the carboxyl group instead of being attached directly to the phenyl radical may be attached to the pyrazolone radical as in aryl-3-carboxypyrazolone. Instead of the above mentioned methyl-ketole-sulphonic acid, other sulpho or carboxy indole derivatives may be used.

Dyes made according to the process described and illustrated above have an unusual affinity for cotton, and show a very ood fastness to light. They are adapted or direct application by the ordinary methods.

I claim:

1. The process of producing a disazo dye which comprises coupling an amino-benzoylamido-benzoyl-2-amid0 5 naphthol 7 -sul phonic acid to an aryl diazo compound free from both sulpho and carboxyl groups, diazotizing the resulting compound and combining it with a sulpho or carboxyl aryl compound containing' a pyrazolone or indole radical.

2. The process of producing a diazo dye which comprises first diazotizing an arylamino mono-azo compound prepared by cou pling an aryl diazo compound free from both sulpho and carboxy groups with an aminobenzoyl amido-benzoyl-2-amido-5-naphthol- 7-sulphonic acid, and then coupling the resulting diazo-monoazo compound to a compound having the grouping and adapted to form with the diazo-monoazo amino benzoyl amido benzoyl 2-amido-5- naphthol-'T-sulphonic acid and then coupling the resulting diazo-monoazo compound to an aryl-pyrazolone compound containing in the aryl1 nucleus an acid group adapted to form a sa t.

4. The process of producing a disazo dye which comprises first diazotizing an arylaniino monoazo compound prepared by coupling an aryl diazo compound free from both sulpho and carboxy groups with an aminobenzoyl-amido-benzoyl-2-amido-5-naphthol 7-sulphonic acid, and then coupling the resulting diazo-monoazo compound to a sulpho-aryl-pyrazolone.

5. The process of preparing a disazo dye which comprises diazotizing aniline, coupling the diazo compound with p-amino-benzoyl-pamido-benzoyl-2-amido-5-naphthol -7 sulphonic acid to obtain amonoazo compound, diazotizing said compound and coupling the resulting 'diazo-monoazo compound to' psulpho-phenyl-methyl-pyrazolone.

6. A disazo dye characterized by yielding on reduction with stannous chloride 2- (amino-benzoyl-amido benzoyl amido) 5 hydroxy 6 amino -naphthalene 7 sulphonic acid and p-sulpho-phenyl-methyl-aminopyrazolone. 1

7. A disazo dye comprising the grouping benzoyl amidobenzoyl-2-amido-5-naphthol- 7-sulphonic acid coupled with an aryl diazo radical free from both sulpho and carboxyl groups, said grouping being also coupled with an aryl pyrazolone or indole radical containing an acid group adapted to form a salt.

8. A disazo dye comprising the grouping benzoyl amido-benzoyl-2-am1do-5-naphtho1- 7-sulphonic acid coupled with an aryl diazo compound free from both sulpho and carboxy groups, said grouping being also coupled with an aryl (pyrazolone containing an acid group and a apted to form therewith an orange to brown disazo dye.

9. A disazo dye comprising the grouping benzoyl amido-benzoyl-Q-amido-5-naphthol 7 -sulphonic acid coupled with an aryl diazo compound free from both sulpho and carboxy' groups, said grouping being also coupled with a sulpho-aryl-pyrazolone.

10. A disazo dye comprising the grouping benzoyl amido-benzoyl-Q-amido-5-naphthol- 7-sulphonic acid coupled with an aryl diazo compound free from both sulpho and carboxy groups, said grouping being also coupled with an aryl-pyrazolone compound containing in the aryl nucleus an acid group adapted to form a salt.

11. A disazo dye comprising the grouping benzoyl amido-benzoyl-2-amido-5-naphthol- 7-sulphonic acid coupled with an aryl diazo radical free from Both sulpho and carboxyl with a phenyl pyrazolone containing a sulpho or carboxyl group.

benzoyl amido-benzoyl-2-amido-5-naphthol- 7 -sulphonic acid coupled with an aryl diazo groups, said cups, said grouping being also coupled with a p-sul ou ing beln 12. A disazo dye comprising the grouping dyestufi set forth in claim 7.

HENRY JORDAN.

Certificate of Correction.

Granted August 13, 1929, to

Patent No. 1,724,660.

HENRY JORDAN It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, after line 15, strike out the formula andinsert instead Ike-0hr page 3, line 41, claim 2, for the word diazo read disazo; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 17th day of September, A. D. 1929.

[shim] M. J. MOORE,

Acting Commissioner ,0f Patents.

radical free from both sulpho and carhoxyl also coupled 1 enyl-met yl-pyrazolone. 13. A texti e material colored with the In testimony whereof I aflix my signature. 

